CN102912637B - Carbon fiber sizing agent - Google Patents

Carbon fiber sizing agent Download PDF

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Publication number
CN102912637B
CN102912637B CN201210463139.0A CN201210463139A CN102912637B CN 102912637 B CN102912637 B CN 102912637B CN 201210463139 A CN201210463139 A CN 201210463139A CN 102912637 B CN102912637 B CN 102912637B
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China
Prior art keywords
resin
solvent
carbon fiber
sizing agent
parts
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CN201210463139.0A
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Chinese (zh)
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CN102912637A (en
Inventor
张国良
李艳华
陈秋飞
席玉松
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中复神鹰碳纤维有限责任公司
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Abstract

The invention discloses a carbon fiber sizing agent which is prepared from the following materials in parts by weight: 5-25 parts of phenolic resin, 1-5 parts of blend resin, 0.01-5 parts of antistatic agent and 100 parts of solvent, wherein the phenolic resin is thermoplastic phenolic resin or modified phenolic resin, and the blend resin is thermoplastic resin or thermosetting resin. The carbon fiber sizing agent is prepared through the following steps of: firstly, uniformly mixing the phenolic resin and the blend resin, adding a solvent accounting for 10-20% of the total amount of the solvent, enabling the resin to be dissolved in the solvent, and stirring the obtained mixture into a homogeneous solution at room temperature; and then, adding the antistatic agent into the homogeneous solution, stirring the obtained mixture so as to dissolve the antistatic agent, adding the rest of the solvent, and mixing the obtained product so as to obtain an integral solution, thereby obtaining the carbon fiber sizing agent. The carbon fiber sizing agent disclosed by the invention can be compatible with thermoplastic matrix resin better; the matrix resin can fully wet carbon fibers, thereby directly achieving a stress transfer effect on the fibers and the matrix; and compared with an epoxy resin sizing agent, the interlayer shear strength of a composite material of the carbon fiber sizing agent is increased by 15-20%.

Description

A kind of carbon fiber sizing agent

Technical field

The present invention relates to a kind of carbon fiber sizing agent.

Background technology

Carbon fiber/polymer matrix composites have a series of excellent properties such as high specific strength, high ratio modulus, corrosion-resistant, resistance to ablation, antifatigue and dimensionally stable, are one of representatives of carbon fibre composite, have been widely used in the field such as textile machine, industry.As the matrix material that polymer matrix composites are important, epoxy resin has good cohesiveness, heat resistance, resistance to corrosive chemicals, high strength and the series of advantages such as easy to process, but the cohesiveness of its solidfied material and fiber is poor, easy to crack, be difficult to meet growing engineering requirement.For adapting to the demand in market, be that the carbon fibre composite of matrix is concerned more and more with thermoplastic resin, in carbon fiber/polymer matrix composites, boundary layer between fiber and matrix plays an important role to composite materials property, good interface cohesion adds the integrality of composite structure, load is made effectively to be delivered on fiber by matrix resin, thus make fiber really play carrying effect, but carbon fiber is crisp, surface energy is low, edge active carbon atom is few, poor with the wettability of matrix resin.So polymer transitional interlayer must be introduced between carbon fiber and matrix resin, i.e. starching process, its surface energy is increased, improves the wettability of carbon fiber and matrix resin.

Current most study be based on the carbon fiber sizing agent of epoxy resin film forming agent, as US4751258, US4420512, US5688554, but carbon fiber is in the preparation process strengthening thermoplastic resin, and there will be obvious phenomenon of phase separation, composite property significantly declines.

Summary of the invention

Technical problem to be solved by this invention is for the deficiencies in the prior art, the performance provide a kind of raw material prescription just for rationally, cost is low, effectively improving carbon fiber, can have the carbon fiber sizing agent of good compatibility with thermoplastic resin simultaneously.

Technical problem to be solved by this invention is realized by following technical scheme.The present invention is a kind of carbon fiber sizing agent, be characterized in, it is made up of the material of following weight proportion: phenolic resins 5 ~ 25, composite resin 1 ~ 5, antistatic additive 0.01 ~ 5, solvent 100, and wherein said phenolic resins is novolac resin or phenol-formaldehyde resin modified; Described composite resin is thermoplastic resin or thermosetting resin,

Its preparation process is as follows: first by phenolic resins and the mixing of composite resin, add the solvent of solvent total amount 10 ~ 20%, make it to be dissolved in solvent, stirred at ambient temperature becomes homogeneous phase solution; In homogeneous phase solution, add antistatic additive again, stirring and dissolving, add remaining solvent, stir and make it into the solution be integrated, can obtain.

In above-described carbon fiber sizing agent technical scheme, preferred technical scheme or feature are further:

1, described phenol-formaldehyde resin modified is POLYPROPYLENE GLYCOL ethylidene ether modification phenolic resins or polyamide modified phenolic resins.

2, described thermoplastic resin is polyamide, polyvinyl alcohol resin, polyamic acid resin or polyamide-imide resin.

3, described thermosetting resin is unsaturated polyester resin or epoxy resin.

4, described antistatic additive is the two maleic mono-ester of polyethylene glycol methacrylic acid copolymer body, polyether ester amides, polyether ester acetamide, polyethylene glycol oxide, epoxypropane copolymerization thing or polyethylene glycol.

5, described solvent is acetone, ethanol or deionized water.

Carbon fiber sizing agent of the present invention significantly improves the adhesive property of fiber and matrix, serves and well strengthens effect; Simultaneously can compatibility good with thermoplastic resin, matrix resin fully can soak carbon fiber, directly plays Stress transmit effect, compared with epoxy resin sizing agent at fiber and matrix, its composite materials property is promoted greatly, and the interlaminar shear strength of composite improves 15-20%;

The preparation method of carbon fiber sizing agent of the present invention is simple, and effective, production efficiency is high, and cost is low, and by changing the proportioning of component in sizing agent, can be applied to different thermoplastic resin matrix.

Detailed description of the invention

Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.

Embodiment 1, a kind of carbon fiber sizing agent, be characterized in, it is made up of the material of following weight proportion: phenolic resins 5 ~ 25, composite resin 1 ~ 5, antistatic additive 0.01 ~ 5, solvent 100, and wherein said phenolic resins is novolac resin or phenol-formaldehyde resin modified; Described composite resin is thermoplastic resin or thermosetting resin,

Its preparation process is as follows: first by phenolic resins and the mixing of composite resin, add the solvent of solvent total amount 10 ~ 20%, make it to be dissolved in solvent, stirred at ambient temperature becomes homogeneous phase solution; In homogeneous phase solution, add antistatic additive again, stirring and dissolving, add remaining solvent, stir and make it into the solution be integrated, can obtain.

Described phenol-formaldehyde resin modified is POLYPROPYLENE GLYCOL ethylidene ether modification phenolic resins or polyamide modified phenolic resins; Described thermoplastic resin is polyamide, polyvinyl alcohol resin, polyamic acid resin or polyamide-imide resin; Described thermosetting resin is unsaturated polyester resin or epoxy resin; Described antistatic additive is the two maleic mono-ester of polyethylene glycol methacrylic acid copolymer body, polyether ester amides, polyether ester acetamide, polyethylene glycol oxide, epoxypropane copolymerization thing or polyethylene glycol; Described solvent is acetone, ethanol or deionized water.

Embodiment 2, a kind of carbon fiber sizing agent, it is made up of novolac resin, polyvinyl alcohol resin, polyether ester amides and acetone, weight proportion is 5:1:0.5:100, during making, be that the novolac resin of 5 parts mixes with the polyvinyl alcohol resin of weight fraction 1 part by weight fraction, first add the solvent acetone of 30 parts, stirring at room temperature makes it abundant dissolving, continue to stir and add the antistatic additive polyether ester amides (PEEA) that weight fraction is 0.5 part, add remaining 70 parts of acetone after mixing, mix homogeneous after prepare carbon fiber sizing agent.

Containing slurry weight fraction with the carbon fiber of this sizing agent starching is 1.8%, carbon fiber carries out twin-screw reactive extrursion and prepares fibre reinforced polyformaldehyde (POM) polymer matrix composites, granulation is carried out after the abundant stirring of high mixer, injection machine injection mo(u)lding, mechanical experimental results is as follows: TENSILE STRENGTH 130Mpa, elastic modelling quantity 14000Mpa, bending strength 213Mpa, bending modulus 10108Mpa, impact strength 19KJ/m 2, Rockwell hardness 120HRR.

Embodiment 3, a kind of carbon fiber sizing agent, it is made up of novolac resin, polyamide, polyether ester amides and acetone, weight proportion is 5:1.5:0.4:100, during making, be that the novolac resin of 4 parts mixes with the polyamide of weight fraction 1.5 parts by weight fraction, first add the solvent acetone of 60 parts, stirring at room temperature makes it abundant dissolving, continue to stir and add the antistatic additive polyether ester amides (PEEA) that weight fraction is 0.4 part, add remaining 40 parts of acetone after mixing, mix homogeneous after prepare carbon fiber sizing agent.

Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 1.6%, carbon fiber carries out twin-screw reactive extrursion and prepares fibre reinforced PA66 polymer matrix composites, granulation is carried out after the abundant stirring of high mixer, injection machine injection mo(u)lding, mechanical experimental results is as follows: TENSILE STRENGTH 151Mpa, elastic modelling quantity 9155Mpa, bending strength 199.8Mpa, bending modulus 7755.5Mpa, impact strength 22KJ/m 2, Rockwell hardness 117HRR.

Embodiment 4, a kind of carbon fiber sizing agent, it is made up of polyamide modified phenolic resins, epoxy resin, polyether ester acetamide and acetone, weight proportion is 10:2:0.6:100, during making, be that the polyamide modified phenolic resins of 10 parts mixes with the epoxy resin of weight fraction 2 parts by weight fraction, first add the solvent acetone of 50 parts, stirring at room temperature makes it abundant dissolving, continue to stir and add the antistatic additive polyether ester acetamide that weight fraction is 0.6 part, add remaining 40 parts of acetone after mixing, mix homogeneous after prepare carbon fiber sizing agent.

Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 1.3%, carbon fiber carries out twin-screw reactive extrursion and prepares fibre reinforced PA6 polymer matrix composites, granulation is carried out after the abundant stirring of high mixer, injection machine injection mo(u)lding, mechanical experimental results is as follows: TENSILE STRENGTH 145Mpa, elastic modelling quantity 9256Mpa, bending strength 220.3Mpa, bending modulus 8976.8Mpa, impact strength 21KJ/m 2, Rockwell hardness 123HRR.

Embodiment 5, a kind of carbon fiber sizing agent, it is by POLYPROPYLENE GLYCOL ethylidene ether modification phenolic resins, polyamic acid resin, polyether ester amides and acetone are made, weight proportion is 6:2:0.45:100, during making, be that the POLYPROPYLENE GLYCOL ethylidene ether modification phenolic resins of 6 parts mixes with the polyamic acid resin of weight fraction 2 parts by weight fraction, first add the solvent acetone of 80 parts, stirring at room temperature makes it abundant dissolving, continue to stir and add the antistatic additive polyether ester amides PEEA that weight fraction is 0.45 part, remaining 20 parts of acetone are added after mixing, prepare the carbon fiber sizing agent that mixing is homogeneous.

Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 1.66%, carbon fiber carries out twin-screw reactive extrursion and prepares fibre reinforced polyformaldehyde (POM) polymer matrix composites, granulation is carried out after the abundant stirring of high mixer, injection machine injection mo(u)lding, mechanical experimental results is as follows: TENSILE STRENGTH 148Mpa, elastic modelling quantity 10123Mpa, bending strength 212.5Mpa, bending modulus 10156Mpa, impact strength 21KJ/m 2, Rockwell hardness 123HRR.

Embodiment 6, a kind of carbon fiber sizing agent, it is by novolac resin, polyamide-imide resin, polyether ester acetamide and ethanol, weight proportion is 5:2:0.3:100, during making, be that the novolac resin of 5 parts mixes with the polyamide-imide resin of weight fraction 2 parts by weight fraction, first add the etoh solvent of 20 parts, stirring at room temperature makes it abundant dissolving, continue to stir and add the antistatic additive polyether ester acetamide that weight fraction is 0.3 part, add remaining 80 parts of ethanol after mixing, prepare the carbon fiber sizing agent that mixing is homogeneous.

Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 1.56%, carbon fiber carries out twin-screw reactive extrursion and prepares fibre reinforced PC polymer matrix composites, granulation is carried out after the abundant stirring of high mixer, injection machine injection mo(u)lding, mechanical experimental results is as follows: TENSILE STRENGTH 128Mpa, elastic modelling quantity 9132Mpa, bending strength 202.7Mpa, bending modulus 7643Mpa, impact strength 18KJ/m 2, Rockwell hardness 115HRR.

Embodiment 7, a kind of carbon fiber sizing agent, it is by POLYPROPYLENE GLYCOL ethylidene ether modification phenolic resins, polyamide-imide resin, polyethylene glycol oxide and deionized water are made, weight proportion is 10:3:1:100, during making, be that the POLYPROPYLENE GLYCOL ethylidene ether modification phenolic resins of 10 parts mixes with the polyamide-imide resin of weight fraction 3 parts by weight fraction, first add the solvent deionized water of 70 parts, stirring at room temperature makes it abundant dissolving, continue to stir and add the antistatic additive polyethylene glycol oxide that weight fraction is 1 part, remaining 30 parts of deionized waters are added after mixing, prepare the carbon fiber sizing agent that mixing is homogeneous.

With after this sizing agent starching carbon fiber containing slurry weight fraction be 1.66%, carbon fiber carries out twin-screw reactive extrursion and prepares fibre reinforced polyformaldehyde (POM) polymer matrix composites, granulation is carried out after the abundant stirring of high mixer, injection machine injection mo(u)lding, mechanical experimental results is as follows: TENSILE STRENGTH 112Mpa, elastic modelling quantity 8975Mpa, bending strength 187.6Mpa, bending modulus 6698.5Mpa, impact strength 18.5KJ/m 2, Rockwell hardness 97HRR.

Claims (1)

1. a carbon fiber sizing agent, it is characterized in that: it is made up of the material of following weight proportion: phenolic resins 5 ~ 25, composite resin 1 ~ 5, antistatic additive 0.01 ~ 5, solvent 100, wherein said phenolic resins is phenol-formaldehyde resin modified, and described phenol-formaldehyde resin modified is POLYPROPYLENE GLYCOL ethylidene ether modification phenolic resins; Described composite resin is thermoplastic resin or thermosetting resin; Antistatic additive is the two maleic mono-ester of polyethylene glycol methacrylic acid copolymer body, polyether ester amides, polyethylene glycol oxide, epoxypropane copolymerization thing or polyethylene glycol; Solvent is acetone, ethanol or deionized water;
Thermoplastic resin is polyamide, polyvinyl alcohol resin, polyamic acid resin or polyamide-imide resin;
Thermosetting resin is unsaturated polyester resin or epoxy resin,
Its preparation process is as follows: first by phenolic resins and the mixing of composite resin, add the solvent of solvent total amount 10 ~ 20%, make it to be dissolved in solvent, stirred at ambient temperature becomes homogeneous phase solution; In homogeneous phase solution, add antistatic additive again, stirring and dissolving, add remaining solvent, stir and make it into the solution be integrated, can obtain.
CN201210463139.0A 2012-11-16 2012-11-16 Carbon fiber sizing agent CN102912637B (en)

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CN103321050B (en) * 2013-06-07 2015-04-22 张家港市德宝化工有限公司 In-bath crease-resisting agent used in polyester fiber, and preparation method thereof
CN104420204B (en) * 2013-09-10 2016-08-10 济南大学 A kind of carbon fiber water soluble epoxy sizing agent
CN103469588B (en) * 2013-09-12 2015-09-09 天津大学 The preparation method of the agent of sisal fiber surface size and sisal fiber composite
CN104562698A (en) * 2013-10-11 2015-04-29 中国石油化工股份有限公司 Preparation method of sizing agent of carbon fibers for reinforcement of thermoplastic resin
ES2738324T3 (en) * 2013-12-23 2020-01-22 Cytec Ind Inc Carbon fibers and high performance fibers for compound applications
CN105369630A (en) * 2015-12-11 2016-03-02 四川大学 Waterborne epoxy emulsion type sizing agent for carbon fiber and preparation method thereof
CN107400489A (en) * 2017-06-30 2017-11-28 长兴华悦耐火材料厂 A kind of modified phenolic resin binder
CN107353020A (en) * 2017-06-30 2017-11-17 长兴泓矿炉料有限公司 A kind of composite refractory brick and preparation method thereof
CN107285784A (en) * 2017-06-30 2017-10-24 长兴华悦耐火材料厂 A kind of preparation method of refractory fibre bonding agent
CN108547151A (en) * 2018-03-30 2018-09-18 王景硕 A kind of aqueous epoxy resins carbon fiber sizing agent
CN109881486B (en) * 2019-02-19 2020-06-09 北京化工大学 Hyperbranched emulsifier and preparation method thereof
CN110528264A (en) * 2019-09-11 2019-12-03 北京化工大学 A kind of high modulus carbon fiber and preparation method thereof as thermoplastic resin based composite material reinforcement

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EP1241379A1 (en) * 2001-03-16 2002-09-18 THE GOODYEAR TIRE & RUBBER COMPANY Power transmission belt containing chopped carbon fiber
CN101007433A (en) * 2006-01-25 2007-08-01 固特异轮胎和橡胶公司 Curing sleeve reinforced with chopped carbon fibers

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